Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method for discharging a liquid from a recess on the surface of a substrate by utilizing dew condensation.SOLUTION: The substrate processing method includes a water repellent agent supplying step of supplying a water repellent agent-containing liquid to the surface of the substrate, the water repellent agent-containing liquid increasing a contact angle of water with respect to a horizontal smooth surface made of the same material as an end face of a convex portion of a pattern to a value exceeding 90 degrees, a water supplying step of supplying a water-containing liquid to the surface of the substrate after the water repellent agent-containing liquid is supplied to the surface of the substrate, a water removing step of removing the water-containing liquid from the surface of the substrate to expose at least a part of the surface of the substrate, a condensation step of generating condensation on the surface of the substrate to attach water droplets to the surface of the substrate, and a drying step of drying the surface of the substrate by removing the water droplets from the surface of the substrate.SELECTED DRAWING: Figure 7

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing substrates, including, for example, semiconductor wafers, substrates for FPDs (Flat Panel Displays) such as liquid crystal displays and organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells. [Background technology]

[0002] Patent Document 1 discloses supplying a water-repellent-containing liquid, a hydrophobic liquid, and a hydrophilic liquid to a substrate in that order, and then removing the internal liquid containing the hydrophilic liquid from the recessed portion of the substrate. Patent Document 1 states that "the water-repellent-containing liquid is, for example, a silylation liquid containing a silylation agent and a solvent," "the hydrophobic liquid is, for example, an organic solvent such as isopropanol (IPA)," and "the hydrophilic liquid is, for example, carbonated water." [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-076165 Summary of the Invention [Problem to be solved by the invention]

[0004] At least one embodiment of the present invention provides a substrate processing method and apparatus that utilizes condensation to drain liquid from recesses in the surface of the substrate. [Means for solving the problem]

[0005] One embodiment of the present invention provides a substrate processing method for processing a substrate having a surface formed with a pattern including convex portions and concave portions, the substrate processing method including: a water-repellent supplying step of supplying a water-repellent-containing liquid to the surface of the substrate, the water-repellent-containing liquid increasing the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees; a water-supplying step of supplying a water-containing liquid to the surface of the substrate after supplying the water-repellent-containing liquid to the surface of the substrate; a water-removing step of removing the water-containing liquid from the surface of the substrate to expose at least a portion of the surface of the substrate; a condensation step of causing condensation on the surface of the substrate to cause water droplets to adhere to the surface of the substrate; and a drying step of removing the water droplets from the surface of the substrate to dry the surface of the substrate.

[0006] In the above embodiment, at least one of the following features may be added to the substrate processing method.

[0007] The condensation step includes a step of causing condensation to occur on the surface of the substrate, thereby causing the water droplets to adhere to at least the inner surface of the recess.

[0008] The drying step includes a step of starting to remove the water droplets from the surface of the substrate when at least a portion of the recess is filled with air and the water droplets are supported by the air in the recess and the protrusion.

[0009] The condensation step includes a step of cooling the substrate.

[0010] The condensation step includes a step of cooling the substrate while keeping the substrate stationary.

[0011] The substrate processing method further includes a post-water-repellent hydrophobic liquid supplying step of supplying a hydrophobic liquid that is soluble in the water-repellent agent-containing liquid to the surface of the substrate, thereby replacing the water-repellent agent-containing liquid on the surface of the substrate with the hydrophobic liquid, and a post-water-repellent amphipathic liquid supplying step of supplying an amphipathic liquid that has a higher water solubility than the hydrophobic liquid and is soluble in the hydrophobic liquid to the surface of the substrate, thereby replacing the hydrophobic liquid on the surface of the substrate with the amphipathic liquid, and the water supplying step is a step of supplying the water-containing liquid that has a higher surface tension than the amphipathic liquid and is soluble in the amphipathic liquid to the surface of the substrate, thereby replacing the amphipathic liquid on the surface of the substrate with the water-containing liquid.

[0012] The substrate processing method further includes a chemical liquid supplying step of supplying, to the surface of the substrate, a chemical liquid that oxidizes the surface of the substrate; a rinsing liquid supplying step of supplying, to the surface of the substrate, the water-containing liquid as a rinsing liquid, thereby replacing the chemical liquid on the surface of the substrate with the water-containing liquid; a pre-water-repellent amphipathic liquid supplying step of supplying, to the surface of the substrate, an amphipathic liquid that is soluble in the water-containing liquid, thereby replacing the water-containing liquid on the surface of the substrate with the amphipathic liquid; and a pre-water-repellent hydrophobic liquid supplying step of supplying, to the surface of the substrate, a hydrophobic liquid that has a lower water solubility than the amphipathic liquid and is soluble in the amphipathic liquid, thereby replacing the amphipathic liquid on the surface of the substrate with the hydrophobic liquid, and the water-repellent agent supplying step is a step of supplying the water-repellent agent-containing liquid to the surface of the substrate, thereby replacing the hydrophobic liquid on the surface of the substrate with the water-repellent agent-containing liquid.

[0013] Another embodiment of the present invention includes a substrate holder for holding a substrate having a pattern including convex portions and concave portions formed on its surface; at least one nozzle for individually discharging a plurality of processing liquids, the processing liquids including a water-containing liquid and a water-repellent-containing liquid, which increase the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees, onto the surface of the substrate held by the substrate holder; at least one valve for individually discharging the plurality of processing liquids from the at least one nozzle; at least one liquid removal actuator for removing the processing liquids from the surface of the substrate held by the substrate holder by moving the substrate to expose at least a portion of the surface of the substrate; and a liquid removal actuator for causing condensation to form on the surface of the substrate held by the substrate holder, thereby causing water droplets to adhere to the surface of the substrate. a control device that controls the at least one valve, the liquid removal actuator, and the condensation generator, wherein the control device executes a water-repellent supplying step of supplying the water-repellent-containing liquid to the surface of the substrate; a water supplying step of supplying the water-containing liquid to the surface of the substrate after supplying the water-repellent-containing liquid to the surface of the substrate; a water removing step of removing the water-containing liquid from the surface of the substrate by the at least one liquid removal actuator to expose at least a part of the surface of the substrate; a condensation step of causing condensation to occur on the surface of the substrate to cause water droplets to adhere to the surface of the substrate; and a drying step of removing the water droplets from the surface of the substrate by the at least one liquid removal actuator to dry the surface of the substrate.

[0014] In the above embodiment, at least one of the following features may be added to the substrate processing apparatus.

[0015] The condensation step includes a step of causing condensation to occur on the surface of the substrate, thereby causing the water droplets to adhere to at least the inner surface of the recess.

[0016] The drying step includes a step of starting to remove the water droplets from the surface of the substrate when at least a portion of the recess is filled with air and the water droplets are supported by the air in the recess and the protrusion.

[0017] The condensation step includes a step of cooling the substrate.

[0018] The condensation step includes a step of cooling the substrate while keeping the substrate stationary.

[0019] The at least one nozzle individually discharges a plurality of processing liquids including the water-repellent-containing liquid, a hydrophobic liquid that is soluble in the water-repellent-containing liquid, an amphipathic liquid that has a higher solubility of water than the hydrophobic liquid and is soluble in the hydrophobic liquid, and the water-containing liquid that has a higher surface tension than the amphipathic liquid and is soluble in the amphipathic liquid, and the control device performs the water-repellent supplying process, a post-water-repellent hydrophobic liquid supplying process of supplying the hydrophobic liquid to the surface of the substrate to replace the water-repellent-containing liquid on the surface of the substrate with the hydrophobic liquid, a post-water-repellent amphipathic liquid supplying process of supplying the amphipathic liquid to the surface of the substrate to replace the hydrophobic liquid on the surface of the substrate with the amphipathic liquid, and the water supplying process of supplying the water-containing liquid to the surface of the substrate to replace the amphipathic liquid on the surface of the substrate with the water-containing liquid.

[0020] The at least one nozzle individually discharges a plurality of processing liquids including the water-repellent-agent-containing liquid, the water-containing liquid, a chemical liquid that oxidizes the surface of the substrate, an amphipathic liquid that dissolves in the water-containing liquid, and a hydrophobic liquid that has a lower solubility of water than the amphipathic liquid and dissolves in the amphipathic liquid, and the control device controls a chemical liquid supplying step of supplying the chemical liquid to the surface of the substrate, and a rinsing liquid supplying step of supplying the water-containing liquid as a rinsing liquid to the surface of the substrate, thereby replacing the chemical liquid on the surface of the substrate with the water-containing liquid. a supplying step, a pre-water-repellent amphipathic liquid supplying step in which the amphipathic liquid is supplied to the surface of the substrate to replace the water-containing liquid on the surface of the substrate with the amphipathic liquid, a pre-water-repellent hydrophobic liquid supplying step in which the hydrophobic liquid is supplied to the surface of the substrate to replace the amphipathic liquid on the surface of the substrate with the hydrophobic liquid, and a water-repellent agent supplying step in which the water-repellent agent-containing liquid is supplied to the surface of the substrate to replace the hydrophobic liquid on the surface of the substrate. [Brief explanation of the drawings]

[0021] [Figure 1A] 1 is a schematic plan view showing a layout of a single-wafer type substrate processing apparatus according to an embodiment; [Figure 1B] FIG. 2 is a schematic side view of the substrate processing apparatus. [Figure 2] FIG. 2 is a schematic diagram showing the interior of the processing unit as viewed horizontally. [Figure 3] 3 is a horizontal schematic view of a processing unit different from the processing unit shown in FIG. 2. FIG. [Figure 4] 4 is a schematic top view of a spin chuck and a heating / cooling plate provided in the processing unit shown in FIG. 3. FIG. [Figure 5] FIG. 2 is a block diagram showing an electrical configuration of the substrate processing apparatus. [Figure 6] 1 is a schematic cross-sectional view showing an example of the structure of a substrate to be processed by a substrate processing apparatus. [Figure 7] 5A to 5C are process diagrams for explaining an example of substrate processing performed by the substrate processing apparatus. [Figure 8A-C] 8 is a schematic cross-sectional view for explaining an example of processing of the substrate shown in FIG. 7. FIG. [Figure 8D-F] 8 is a schematic cross-sectional view for explaining an example of processing of the substrate shown in FIG. 7. FIG. [Figure 8G-I] 8 is a schematic cross-sectional view for explaining an example of processing of the substrate shown in FIG. 7. FIG. [Figure 9A] FIG. 1 is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in a Wenzel state. [Figure 9B] FIG. 1 is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in a Cassie-Baxter state. [Figure 10] FIG. 10 is a schematic side view of a batch-type substrate processing apparatus according to another embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0022] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0023] 1A is a schematic plan view showing the layout of a single-wafer type substrate processing apparatus 1 according to one embodiment, and FIG.

[0024] 1A, the substrate processing apparatus 1 is a single-wafer processing apparatus that processes disk-shaped substrates W, such as semiconductor wafers, one by one. The substrate processing apparatus 1 includes a load port LP that holds carriers CA that accommodate multiple substrates W, such as FOUPs (Front-Opening Unified Pods), multiple processing units 2 that process the substrates W transferred from the carriers CA on the load port LP with processing fluids, such as processing liquids and processing gases, a transfer system TS that transfers the substrates W between the carriers CA on the load port LP and the multiple processing units 2, an outer wall 1a that forms an enclosed space that houses the multiple processing units 2 and the transfer system TS, and a controller 3 that controls the substrate processing apparatus 1.

[0025] The multiple processing units 2 form multiple towers TW. FIG. 1A shows an example in which four towers TW are formed. As shown in FIG. 1B, the multiple processing units 2 included in one tower TW are stacked one on top of the other. As shown in FIG. 1A, the multiple towers TW form two rows extending in the depth direction of the substrate processing apparatus 1 (left and right directions on the paper surface of FIG. 1A) in a plan view. In a plan view, the two rows face each other via a transport path TP.

[0026] The transport system TS includes an indexer robot IR that loads and unloads substrates W into and from carriers CA on the load port LP, and a center robot CR that loads and unloads substrates W into and from multiple processing units 2. The center robot CR is disposed on the transport path TP. The indexer robot IR is disposed between the load port LP and the center robot CR in a plan view. The indexer robot IR hands over substrates W to the center robot CR and receives substrates W from the center robot CR. The same is true for the center robot CR.

[0027] The indexer robot IR includes one or more hands Hi that support a substrate W horizontally. The hands Hi can move parallel in both the horizontal and vertical directions. The hands Hi can rotate about a vertical line. The hands Hi can load and unload a substrate W to and from a carrier CA on any of the load ports LP, and can transfer a substrate W to and from the center robot CR.

[0028] The center robot CR includes one or more hands Hc that support the substrate W horizontally. The hands Hc can move parallel in both the horizontal and vertical directions. The hands Hc can rotate about a vertical line. The hands Hc can transfer the substrate W to and from the indexer robot IR, and can transport the substrate W into and out of any of the processing units 2.

[0029] Next, the processing unit 2 will be described.

[0030] Fig. 2 is a horizontal schematic view of the interior of the processing unit 2. As shown in Fig. 2, the processing unit 2 includes a chamber 4 that accommodates a substrate W, and a spin chuck 10 that holds one substrate W horizontally within the chamber 4 and rotates the substrate W about a vertical rotation axis A1 that passes through the center of the substrate W.

[0031] The chamber 4 includes a box-shaped partition wall 5 having a passage opening 5b through which the substrate W passes, and a door 6 for opening and closing the passage opening 5b. The FFU 7 (fan filter unit 7) is disposed above an air outlet 5a disposed at the top of the partition wall 5. The FFU 7 constantly supplies clean air (air filtered by a filter) into the chamber 4 through the air outlet 5a. The gas within the chamber 4 is exhausted from the chamber 4 through an exhaust duct 8 connected to the bottom of a processing cup 21 (described later). This constantly creates a downflow of clean air within the chamber 4. The flow rate of the exhaust air discharged into the exhaust duct 8 is changed according to the opening degree of an exhaust valve 9 disposed within the exhaust duct 8.

[0032] The spin chuck 10 includes a disk-shaped spin base 12 held horizontally, a plurality of chuck pins 11 that hold the substrate W horizontally above the spin base 12, and a spin motor 13 that rotates the spin base 12 and the plurality of chuck pins 11 about a rotation axis A1. The spin chuck 10 is not limited to a mechanical chuck that brings the plurality of chuck pins 11 into contact with the edge surface of the substrate W, but may also be a vacuum chuck that holds the substrate W horizontally by adsorbing the back surface (lower surface) of the substrate W, which is not a device formation surface, to an upper surface 12u of the spin base 12. When the spin chuck 10 is a mechanical chuck, the plurality of chuck pins 11 correspond to a substrate holder. When the spin chuck 10 is a vacuum chuck, the spin base 12 corresponds to a substrate holder.

[0033] The processing unit 2 includes a cylindrical processing cup 21 that receives the processing liquid splashed from the substrate W. The processing cup 21 includes a plurality of guards 24 that receive the processing liquid discharged outward from the substrate W held on the spin chuck 10, a plurality of cups 23 that receive the processing liquid guided downward by the plurality of guards 24, and a cylindrical outer wall 22 that surrounds the plurality of guards 24 and the plurality of cups 23. Figure 2 shows an example in which four guards 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third guard 24 from the top.

[0034] The guard 24 includes a cylindrical portion 25 that surrounds the spin chuck 10 and an annular ceiling portion 26 that extends obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. The multiple ceiling portions 26 are stacked one on top of the other, and the multiple cylindrical portions 25 are arranged concentrically. The upper end of the annular ceiling portion 26 corresponds to the upper end of the guard 24 that surrounds the substrate W and the spin base 12 in a plan view. The multiple cups 23 are respectively arranged below the multiple cylindrical portions 25. The cups 23 form annular grooves that receive the processing liquid guided downward by the guard 24.

[0035] The processing unit 2 includes an elevation actuator 27 that individually raises and lowers the multiple guards 24. The elevation actuator 27 stops the guards 24 at any position within a range from the upper position to the lower position. FIG. 2 shows a state in which two guards 24 are positioned at the upper position and the remaining two guards 24 are positioned at the lower position. The upper position is a position in which the upper ends of the guards 24 are positioned above the holding position in which the substrate W held by the spin chuck 10 is positioned. The lower position is a position in which the upper ends of the guards 24 are positioned below the holding position.

[0036] An actuator is a device that converts driving energy, such as electrical, fluid, magnetic, thermal, or chemical energy, into mechanical work, i.e., the movement of a tangible object. Actuators include electric motors (rotary motors), linear motors, air cylinders, and other devices. When the movement of the actuator differs from the movement of the object, a motion converter may be provided to convert the movement of the actuator into linear motion or rotation. For example, if the actuator is an electric motor that moves the object linearly, the rotation of the electric motor may be converted into linear motion by a motion converter such as a ball screw and ball nut.

[0037] Processing unit 2 includes a plurality of nozzles that discharge processing fluids such as processing liquid and processing gas toward substrate W held on spin chuck 10. The plurality of nozzles include first chemical liquid nozzle 31a, first rinsing liquid nozzle 31b, second chemical liquid nozzle 31c, second rinsing liquid nozzle 31d, water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g.

[0038] First chemical liquid nozzle 31a and second chemical liquid nozzle 31c are nozzles that eject chemical liquid toward the upper surface of substrate W. First rinsing liquid nozzle 31b and second rinsing liquid nozzle 31d are nozzles that eject rinsing liquid toward the upper surface of substrate W. Water repellent agent nozzle 31e is a nozzle that ejects a water repellent agent-containing liquid toward the upper surface of substrate W. Hydrophobic liquid nozzle 31f is a nozzle that ejects a hydrophobic liquid toward the upper surface of substrate W. Amphipathic liquid nozzle 31g is a nozzle that ejects an amphipathic liquid toward the upper surface of substrate W.

[0039] FIG. 2 shows an example in which the first chemical liquid is DFH (dilute hydrofluoric acid), the second chemical liquid is SC1 (a mixture of ammonia water, hydrogen peroxide, and water), and the rinse liquid is DIW (pure water). DFH is a chemical liquid that removes native silicon oxide films. SC1 is a chemical liquid that removes particles, organic matter, and the like from the substrate W. SC1 is an example of a chemical liquid that oxidizes the top surface of the substrate W.

[0040] First chemical liquid nozzle 31a may be a scan nozzle that moves the collision position of the chemical liquid on substrate W within the upper surface of substrate W, or may be a fixed nozzle that cannot move the collision position of the chemical liquid on substrate W. The same applies to the other nozzles. Figure 2 shows an example in which first chemical liquid nozzle 31a, first rinsing liquid nozzle 31b, second chemical liquid nozzle 31c, second rinsing liquid nozzle 31d, water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g are scan nozzles.

[0041] First chemical liquid nozzle 31a and first rinse liquid nozzle 31b are connected to first nozzle actuator 35a, which moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b in at least one of the vertical and horizontal directions. First chemical liquid nozzle 31a and first rinse liquid nozzle 31b extend downward from first nozzle arm 34a, which extends horizontally within chamber 4. First nozzle actuator 35a moves first nozzle arm 34a, thereby moving first chemical liquid nozzle 31a and first rinse liquid nozzle 31b.

[0042] Second chemical liquid nozzle 31c and second rinse liquid nozzle 31d are connected to second nozzle actuator 35b, which moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d in at least one of the vertical and horizontal directions. Second chemical liquid nozzle 31c and second rinse liquid nozzle 31d extend downward from second nozzle arm 34b, which extends horizontally within chamber 4. Second nozzle actuator 35b moves second nozzle arm 34b, thereby moving second chemical liquid nozzle 31c and second rinse liquid nozzle 31d.

[0043] The water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g are connected to a third nozzle actuator 35c that moves the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in at least one of the vertical and horizontal directions. The water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g extend downward from a third nozzle arm 34c that extends horizontally within the chamber 4. The third nozzle actuator 35c moves the third nozzle arm 34c, thereby moving the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g.

[0044] First nozzle actuator 35a horizontally moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b between a processing position where the processing liquid discharged from first chemical liquid nozzle 31a or first rinse liquid nozzle 31b is supplied to the upper surface of substrate W and a standby position where first chemical liquid nozzle 31a and first rinse liquid nozzle 31b are positioned around processing cup 21 in a plan view. The same applies to second nozzle actuator 35b and rinse liquid actuator. Figure 2 shows a state where water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g are arranged at the processing positions.

[0045] First chemical liquid nozzle 31a is connected to first chemical liquid pipe 32a that guides the first chemical liquid. When first chemical liquid valve 33a attached to first chemical liquid pipe 32a is opened, the outlet of first chemical liquid nozzle 31a continuously discharges the first chemical liquid downward. Similarly, second chemical liquid nozzle 31c is connected to second chemical liquid pipe 32c that guides the second chemical liquid. When second chemical liquid valve 33c attached to second chemical liquid pipe 32c is opened, the outlet of second chemical liquid nozzle 31c continuously discharges the second chemical liquid downward.

[0046] The first chemical liquid may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, hydrogen peroxide, organic acid (e.g., citric acid, oxalic acid, etc.), organic alkali (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and corrosion inhibitor, or may be a liquid other than these. The same applies to the second chemical liquid. The first chemical liquid may be a liquid having the same composition as the second chemical liquid but different from the second chemical liquid in at least one of concentration and temperature.

[0047] Although not shown, first chemical liquid valve 33a includes a valve body with an annular valve seat through which the chemical liquid passes, a valve element movable relative to the valve seat, and an actuator that moves the valve element between a closed position in which the valve element contacts the valve seat and an open position in which the valve element is separated from the valve seat. The same applies to the other valves. The actuator may be a pneumatic actuator, an electric actuator, or another type of actuator. Control device 3 controls the actuator to open and close first chemical liquid valve 33a, etc.

[0048] The first rinse liquid nozzle 31b is connected to a first rinse liquid pipe 32b that guides the first rinse liquid. When a first rinse liquid valve 33b attached to the first rinse liquid pipe 32b is opened, the outlet of the first rinse liquid nozzle 31b continuously discharges the first rinse liquid downward. Similarly, the second rinse liquid nozzle 31d is connected to a second rinse liquid pipe 32d that guides the second rinse liquid. When a second rinse liquid valve 33d attached to the second rinse liquid pipe 32d is opened, the outlet of the second rinse liquid nozzle 31d continuously discharges the second rinse liquid downward.

[0049] The first rinse liquid may be any of pure water (deionized water: DIW), carbonated water, electrolytic ionized water, hydrogen water, ozone water, diluted hydrochloric acid water (for example, about 1 to 100 ppm), and diluted ammonia water (for example, about 1 to 100 ppm), or may be a liquid other than these. The same applies to the second rinse liquid. The first rinse liquid may have the same composition as the second rinse liquid but differ from the second rinse liquid in at least one of the concentration and temperature. The rinse liquid is an example of a water-containing liquid. The water-containing liquid may be a liquid whose water content is 100% or substantially 100% (for example, 99% or more), or may be a liquid containing substances other than water.

[0050] The water repellent nozzle 31e is connected to a water repellent pipe 32e that guides a water repellent-containing liquid. When a water repellent valve 33e attached to the water repellent pipe 32e is opened, the outlet of the water repellent nozzle 31e continuously discharges the water repellent-containing liquid downward. Similarly, the hydrophobic liquid nozzle 31f is connected to a hydrophobic liquid pipe 32f that guides a hydrophobic liquid. When a hydrophobic liquid valve 33f attached to the hydrophobic liquid pipe 32f is opened, the outlet of the hydrophobic liquid nozzle 31f continuously discharges the hydrophobic liquid downward. The amphipathic liquid nozzle 31g is connected to an amphipathic liquid pipe 32g that guides an amphipathic liquid. When an amphipathic liquid valve 33g attached to the amphipathic liquid pipe 32g is opened, the outlet of the amphipathic liquid nozzle 31g continuously discharges the amphipathic liquid downward.

[0051] The hydrophobic liquid is a liquid that dissolves in the water-repellent-containing liquid. The amphipathic liquid is a liquid that dissolves in both the hydrophobic liquid and the water-containing liquid. The amphipathic liquid may also be a liquid that dissolves in the water-repellent-containing liquid. If the solubility of water in the hydrophobic liquid is lower than the solubility of water in the amphipathic liquid, the hydrophobic liquid may also be a liquid that dissolves in the water-containing liquid. The solubility of water in the amphipathic liquid is lower than the solubility of water in the water-containing liquid. The surface tension of the amphipathic liquid is lower than the surface tension of the water-containing liquid. The surface tension of the amphipathic liquid may be equal to, higher than, or lower than the surface tension of the hydrophobic liquid. The surface tension of the hydrophobic liquid may be equal to, higher than, or lower than the surface tension of the water-containing liquid.

[0052] The hydrophobic liquid and the amphipathic liquid may be organic solvents. In this case, the hydrophobic liquid may be at least one of alcohols such as IPA (isopropyl alcohol), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. The same is true for amphiphilic liquids.

[0053] The water-repellent agent-containing liquid is a liquid that modifies the upper surface of the substrate W. The water-repellent agent-containing liquid is a liquid that makes the upper surface of the substrate W hydrophobic. After the water-repellent agent-containing liquid is supplied, the upper surface of the substrate W is a water-repellent surface. As will be described later, the upper surface of the substrate W is a rough surface on which a pattern PA (see FIG. 6) including convex portions P1 and concave portions Q1 is formed. The water-repellent agent-containing liquid is a liquid that increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end surface s1 of the convex portion P1 to a value greater than 90 degrees.

[0054] The water-repellent-containing liquid may be a liquid containing 100% or substantially 100% water-repellent, or may be a liquid containing substances other than the water-repellent. In the latter case, the water-repellent-containing liquid may be a solution containing the water-repellent as a solute and a solvent that dissolves in the water-repellent. In this case, the solvent of the water-repellent-containing liquid may be at least one of the specific examples of organic solvents mentioned above, such as IPA. The solvent contained in the water-repellent-containing liquid may be a liquid having the same composition as the hydrophobic liquid.

[0055] The water repellent agent may be at least one of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDTS), 3-aminopropyltriethoxysilane (APTES), benzyltrichlorosilane (Bn-TS), 11-cyanoundecyltrichlorosilane, 11-iodoundecyltrichlorosilane, 11-bromoundecyltrichlorosilane, 11-chloroundecyltrichlorosilane, and undecyltrichlorosilane (H-UTS). That is, the water repellent agent may be a silylating agent.

[0056] In the following, an example will be described in which the water repellent-containing liquid is a solution containing FDTS as a solute and toluene as a solvent, the hydrophobic liquid is toluene, and the amphipathic liquid is IPA.

[0057] In addition to the first chemical liquid nozzle 31a, the multiple nozzles include a lower surface nozzle 31h that ejects the processing liquid toward the center of the lower surface of the substrate W. The lower surface nozzle 31h includes a disk portion disposed between the upper surface 12u of the spin base 12 and the lower surface of the substrate W, and a cylindrical portion extending downward from the disk portion. The ejection port of the lower surface nozzle 31h opens at the center of the upper surface of the disk portion. When the substrate W is held by the spin chuck 10, the ejection port of the lower surface nozzle 31h faces the center of the lower surface of the substrate W in the vertical direction.

[0058] The lower surface nozzle 31h is connected to a rinse liquid pipe 32h that guides the rinse liquid. FIG. 2 shows an example in which the rinse liquid is pure water. When a rinse liquid valve 33h attached to the rinse liquid pipe 32h is opened, the rinse liquid is continuously discharged upward from the discharge port of the lower surface nozzle 31h. The temperature of the rinse liquid discharged from the lower surface nozzle 31h may be room temperature, or may be higher or lower than room temperature.

[0059] The outer peripheral surface of the lower nozzle 31h and the inner peripheral surface of the spin base 12 form a cylindrical gas flow path that extends vertically. The gas flow path includes a central opening 31i that opens at the center of the upper surface 12u of the spin base 12. The gas flow path is connected to an inert gas pipe 32i that guides inert gas. When an inert gas valve 33i attached to the inert gas pipe 32i is opened, the inert gas is continuously discharged upward from the central opening 31i of the spin base 12.

[0060] When the substrate W is held on the spin chuck 10, the inert gas is discharged from the central opening 31i of the spin base 12. The inert gas flows radially in all directions between the lower surface of the substrate W and the upper surface 12u of the spin base 12. This fills the space between the substrate W and the spin base 12 with the inert gas. The inert gas discharged from the central opening 31i of the spin base 12 is nitrogen gas. The inert gas may be a gas other than nitrogen gas, such as helium gas or argon gas. The temperature of the inert gas discharged from the central opening 31i of the spin base 12 may be room temperature, or may be higher or lower than room temperature.

[0061] Next, a processing unit 2 different from the processing unit 2 shown in FIG. 2 will be described.

[0062] Fig. 3 is a horizontal schematic view of a processing unit 2 different from the processing unit 2 shown in Fig. 2. Fig. 4 is a top schematic view of the spin chuck 10 and the heating / cooling plate 42 provided in the processing unit 2 shown in Fig. 3. Components equivalent to those shown in Fig. 2 are given the same reference numerals as in Fig. 2, and descriptions thereof will be omitted.

[0063] The processing unit 2 shown in Figures 3 and 4 differs from the processing unit 2 shown in Figure 2 in that a heating / cooling plate 42 is provided instead of the lower nozzle 31h. The heating / cooling plate 42 is an example of an electrical device that generates and absorbs heat in response to the supply of power. As shown in Figure 3, the heating / cooling plate 42 is disposed between the substrate W and the spin base 12.

[0064] The heating / cooling plate 42 includes a Peltier element 43 that generates and absorbs heat in response to the supply of power, and an outer case 44 that houses the Peltier element 43. The Peltier element 43 and the outer case 44 are disposed below the substrate W. The Peltier element 43 is connected to wiring (not shown) that supplies a direct current to the Peltier element 43. When the substrate W is supported by the outer case 44, the substrate W is uniformly heated or cooled according to the direction of the direct current supplied to the Peltier element 43. The control device 3 controls the temperature of the substrate W supported by the outer case 44 by switching on and off the supply of direct current to the Peltier element 43 and switching the direction of the direct current supplied to the Peltier element 43.

[0065] The outer case 44 of the heating / cooling plate 42 includes a disk-shaped base portion 45 disposed below the substrate W, and a plurality of hemispherical protrusions 46 protruding upward from the upper surface of the base portion 45. The upper surface of the base portion 45 is parallel to the lower surface of the substrate W and has an outer diameter smaller than the diameter of the substrate W. The plurality of protrusions 46 contact the lower surface of the substrate W at positions spaced above the upper surface of the base portion 45. The plurality of protrusions 46 are disposed at a plurality of positions within the upper surface of the base portion 45 so that the substrate W is supported horizontally. The substrate W is supported horizontally with the lower surface of the substrate W spaced above the upper surface of the base portion 45.

[0066] As shown in FIG. 4, multiple chuck pins 11 are arranged around a heating / cooling plate 42. The center line of the heating / cooling plate 42 is aligned with the rotation axis A1 of the substrate W. Even when the spin chuck 10 rotates, the heating / cooling plate 42 does not rotate. The outer diameter of the heating / cooling plate 42 is smaller than the diameter of the substrate W. The difference between the outer diameter of the heating / cooling plate 42 and the diameter of the substrate W is smaller than the height of the chuck pins 11 (see FIG. 3; the vertical length from the upper surface 12u of the spin base 12 to the upper ends of the chuck pins 11).

[0067] As shown in FIG. 3, the heating / cooling plate 42 is horizontally supported by a support shaft 47 extending downward from the center of the heating / cooling plate 42. The heating / cooling plate 42 is movable up and down relative to the spin base 12. The heating / cooling plate 42 is connected to a lifting actuator 48 via the support shaft 47. The lifting actuator 48 translates the heating / cooling plate 42 up and down between an upper position (position indicated by a solid line in FIG. 3) and a lower position (position indicated by a two-dot chain line in FIG. 3). The upper position is a contact position where the heating / cooling plate 42 comes into contact with the lower surface of the substrate W. The lower position is a proximity position where the heating / cooling plate 42 is spaced apart from the substrate W and is positioned between the lower surface of the substrate W and the upper surface 12u of the spin base 12.

[0068] The lifting actuator 48 positions the heating and cooling plate 42 at any position between the upper position and the lower position. When the substrate W is supported by the multiple chuck pins 11 and the heating and cooling plate 42 is raised to the upper position while the substrate W is released from its grip, the multiple protrusions 46 of the heating and cooling plate 42 come into contact with the underside of the substrate W, and the substrate W is supported by the heating and cooling plate 42. The substrate W is then lifted by the heating and cooling plate 42 and separated upward from the multiple chuck pins 11. When the heating and cooling plate 42 is lowered to the lower position in this state, the substrate W on the heating and cooling plate 42 is placed on the multiple chuck pins 11, and the heating and cooling plate 42 is separated downward from the substrate W. In this manner, the substrate W is transferred between the multiple chuck pins 11 and the heating and cooling plate 42.

[0069] Next, the electrical configuration of the substrate processing apparatus 1 will be described.

[0070] 5 is a block diagram showing the electrical configuration of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control device 3 that controls the electrical and electronic devices provided in the substrate processing apparatus 1. The control device 3 includes at least one computer that can communicate with each other. The computer includes a computer main body 3a and a peripheral device 3d connected to the computer main body 3a.

[0071] The computer main body 3a includes a CPU 3b (central processing unit) that executes various commands, and a memory 3c that stores information to be transmitted and received between the CPU 3b. The peripheral device 3d includes a storage 3e that stores information to be transmitted and received between the memory 3c, such as a program P, a reader 3f that reads information from removable media RM, and a communication device 3g that communicates with other devices such as a host computer HC. The memory 3c and the storage 3e are both examples of storage devices that store information to be transmitted and received between the CPU 3b.

[0072] The control device 3 is connected to an input device 3h and a display device 3i. The input device 3h is operated when an operator such as a user or a maintenance technician inputs information into the substrate processing apparatus 1. The information is displayed on the screen of the display device 3i. The input device 3h may be any one of a keyboard, a pointing device, and a touch panel, or may be a device other than these. The substrate processing apparatus 1 may be provided with a touch panel display that serves as both the input device 3h and the display device 3i.

[0073] The CPU 3b executes a program P stored in the storage 3e. The program P in the storage 3e may be one that has been pre-installed in the control device 3, or may be one that has been sent from a removable medium RM to the storage 3e via a reader 3f, or may be one that has been sent from an external device such as a host computer HC via a communication device 3g to the storage 3e.

[0074] The memory 3c is a volatile memory that retains its memory only when power is supplied. The storage 3e and the removable medium RM are non-volatile memories that retain their memory even when power is not supplied. The storage 3e is, for example, a magnetic storage device such as a hard disk drive. The removable medium RM is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a non-transitory tangible recording medium.

[0075] The storage 3e stores a plurality of recipes RC. The recipes RC are information that specifies the processing content, processing conditions, and processing procedures for the substrates W. The plurality of recipes RC differ from one another in at least one of the processing content, processing conditions, and processing procedures for the substrates W. The control device 3 controls the substrate processing apparatus 1 so that the substrates W are processed in accordance with the recipes RC specified by the host computer HC. The control device 3 is programmed to execute each of the processes described below. The programs P that execute each of the processes described below may be stored in either the storage 3e or the removable medium RM.

[0076] Next, an example of the structure of the substrate W will be described.

[0077] FIG. 6 is a schematic cross-sectional view showing an example of the structure of a substrate W processed by the substrate processing apparatus 1. The substrate W includes a front surface and a back surface that are parallel to each other, and an annular end surface that connects the outer edges of the front surface and the back surface along the entire periphery of the front surface and the back surface. FIG. 6 shows the state in which the front surface of the substrate W faces upward. The front surface of the substrate W corresponds to the upper surface of the substrate W. The front surface of the substrate W is a device formation surface on which devices are formed. The back surface of the substrate W is a non-device formation surface on which devices are not formed. Both the front surface and the back surface of the substrate W may be device formation surfaces.

[0078] The front and back surfaces of the substrate W are flat surfaces parallel to each other. When the pattern PA is formed on the surface of the substrate W, the surface of the substrate W is, strictly speaking, an uneven surface. The thickness direction of the substrate W is a direction perpendicular to the flat surface of the substrate W before the pattern PA is formed, and the surface direction of the substrate W is a direction parallel to the flat surface. In Figure 6, the up-down direction on the paper surface corresponds to the thickness direction of the substrate W, and the left-right direction on the paper surface corresponds to the surface direction of the substrate W. If the pattern PA is on the top surface of the substrate W when the water repellent agent-containing liquid is supplied to the top surface of the substrate W, the pattern PA may be formed before the substrate processing apparatus 1 processes the substrate W, or may be formed while the substrate processing apparatus 1 is processing the substrate W.

[0079] FIG. 6 shows an example of a cross section of a substrate W cut along a plane perpendicular to the flat surface of the substrate W before the pattern PA is formed. In this example, a plurality of protrusions P1 are formed on the surface of a base layer s4 of the substrate W, extending in the thickness direction of the substrate W. The base layer s4 may be part of a disk-shaped semiconductor substrate, or a thin film formed on the substrate. The pattern PA includes a plurality of protrusions P1 and a plurality of recesses Q1. The plurality of protrusions P1 are spaced apart from each other in the surface direction of the substrate W. Two protrusions P1 face each other in the surface direction of the substrate W with a gap between them, forming recesses Q1 recessed in the thickness direction of the substrate W from the tips of the two protrusions P1.

[0080] FIG. 6 shows an example in which the cross section of the protrusion P1 is rectangular and extends in the thickness direction of the substrate W. The protrusion P1 may be cylindrical, prism-shaped, or plate-shaped, or may have other shapes. The recess Q1 may be a hole or a groove. The protrusion P1 may extend in the surface direction of the substrate W rather than in the thickness direction of the substrate W. The width of the protrusion P1 may be constant from the base of the protrusion P1 to the tip of the protrusion P1, or may vary. The width of the recess Q1 may be constant from the bottom of the recess Q1 to the entrance of the recess Q1, or may vary.

[0081] The protrusion P1 may be composed of only one layer, or may be composed of multiple layers stacked in the height direction of the protrusion P1. FIG. 6 shows an example of the former. In the latter case, all layers included in one protrusion P1 may be made of the same or different materials, or some of the layers may be made of the same material different from the rest of the layers. The material of the protrusion P1 may be one or more of a semiconductor, an insulator, and a metal, or may be other materials. The material of the end surface s1 of the protrusion P1 may be a silicon-containing material such as silicon dioxide, or may be other materials.

[0082] The surface of the pattern PA includes the surfaces of the convex portions P1 and the inner surfaces of the concave portions Q1. The surface of the convex portions P1 includes end faces s1 corresponding to the tips of the convex portions P1 and side faces s2 extending from the end faces s1 to the bases of the convex portions P1. The end faces s1 of the convex portions P1 correspond to the tip and top surfaces of the convex portions P1. The end faces s1 of the multiple convex portions P1 are arranged on a single plane. The end faces s1 of the multiple convex portions P1 correspond to part or all of the upper surface of the substrate W. The inner surfaces of the concave portions Q1 include bottom faces s3 corresponding to the bottom of the concave portions Q1 and side faces extending from the bottom faces s3 to the entrances of the concave portions Q1. The side faces of the concave portions Q1 may also serve as the side faces s2 of the convex portions P1, or may be different from the side faces s2. Figure 6 shows an example of the former. The side faces of the concave portions Q1 form the entrances of the concave portions Q1.

[0083] Next, an example of processing of the substrate W performed by the substrate processing apparatus 1 will be described.

[0084] Fig. 7 is a process diagram for explaining an example of processing of a substrate W performed by the substrate processing apparatus 1. In the following, Fig. 2 will be referred to. Fig. 7 will also be referred to as appropriate.

[0085] When the substrate W is processed by the substrate processing apparatus 1, a loading step (step S1 in FIG. 7) of loading the substrate W into the chamber 4 is performed.

[0086] Specifically, with all guards 24 in the lower position and all scan nozzles in the standby position, the center robot CR (see FIG. 1A) places the substrate W on the hand Hc onto the chuck pins 11 with the surface of the substrate W facing upward, and then retracts the hand Hc from the inside of the chamber 4. Once the substrate W is placed on the chuck pins 11, all of the chuck pins 11 are pressed against the edge surface of the substrate W, and the substrate W is held by the spin chuck 10. Then, the spin motor 13 is driven, and the substrate W begins to rotate (step S2 in FIG. 7).

[0087] Next, a first chemical liquid supplying step (step S3 in FIG. 7) of supplying DHF, which is an example of a first chemical liquid, onto the upper surface of the substrate W is performed.

[0088] Specifically, with at least one guard 24 in the upper position, first nozzle actuator 35a moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b from the standby position to the processing position. Then, first chemical liquid valve 33a is opened, and first chemical liquid nozzle 31a begins to discharge DHF. After a predetermined time has elapsed since first chemical liquid valve 33a was opened, first chemical liquid valve 33a is closed, and the discharge of DHF is stopped.

[0089] The DHF discharged from first chemical liquid nozzle 31a collides with the upper surface of substrate W, which is rotating at the first chemical liquid supply speed, and then flows outward along the upper surface of substrate W. As a result, DHF is supplied to the entire upper surface of substrate W, and a liquid film of DHF is formed covering the entire upper surface of substrate W. While first chemical liquid nozzle 31a is discharging DHF, first nozzle actuator 35a may move first nozzle arm 34a to move the collision position of DHF with the upper surface of substrate W between the center and the outer periphery, or may keep the collision position stationary at the center. Whether or not the collision position is moved applies similarly to the processing liquid supplied to the upper surface of substrate W after DHF.

[0090] Next, a first rinsing liquid supplying step (step S4 in FIG. 7) is performed in which pure water, which is an example of a first rinsing liquid, is supplied to the upper surface of the substrate W.

[0091] Specifically, with at least one guard 24 in the upper position and first chemical liquid nozzle 31a and first rinse liquid nozzle 31b in the processing position, first rinse liquid valve 33b is opened, and first rinse liquid nozzle 31b begins to discharge deionized water. The deionized water discharged from first rinse liquid nozzle 31b collides with the upper surface of substrate W, which is rotating at the first rinse liquid supply speed, and then flows outward along the upper surface of substrate W. As a result, DHF on substrate W is replaced with deionized water, and a liquid film of deionized water is formed covering the entire upper surface of substrate W. When a predetermined time has elapsed since first rinse liquid valve 33b was opened, first rinse liquid valve 33b is closed. Then, first nozzle actuator 35a moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b to the standby position.

[0092] Next, a second chemical liquid supplying step (step S5 in FIG. 7) of supplying SC1, which is an example of a second chemical liquid, to the upper surface of the substrate W is performed.

[0093] Specifically, with at least one guard 24 in the upper position, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d from the standby position to the processing position. Then, second chemical liquid valve 33c is opened, and second chemical liquid nozzle 31c begins to discharge SC1. SC1 discharged from second chemical liquid nozzle 31c collides with the upper surface of substrate W, which is rotating at the second chemical liquid supply speed, and then flows outward along the upper surface of substrate W. This replaces the pure water on substrate W with SC1, forming a liquid film of SC1 that covers the entire upper surface of substrate W. When a predetermined time has elapsed since second chemical liquid valve 33c was opened, second chemical liquid valve 33c is closed.

[0094] Next, a second rinsing liquid supplying step (step S6 in FIG. 7) is performed in which pure water, which is an example of a second rinsing liquid, is supplied to the upper surface of the substrate W.

[0095] Specifically, with at least one guard 24 in the upper position and second chemical liquid nozzle 31c and second rinse liquid nozzle 31d in the processing position, second rinse liquid valve 33d is opened, and second rinse liquid nozzle 31d begins to discharge deionized water. The deionized water discharged from second rinse liquid nozzle 31d collides with the upper surface of substrate W, which is rotating at the second rinse liquid supply speed, and then flows outward along the upper surface of substrate W. As a result, DHF on substrate W is replaced with deionized water, and a liquid film of deionized water is formed covering the entire upper surface of substrate W. When a predetermined time has elapsed since second rinse liquid valve 33d was opened, second rinse liquid valve 33d is closed. Then, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d to the standby position.

[0096] Next, a pre-water-repellent amphipathic liquid supplying step (step S7 in FIG. 7) is performed in which IPA, which is an example of an amphipathic liquid, is supplied onto the upper surface of the substrate W.

[0097] Specifically, with at least one guard 24 in the upper position, third nozzle actuator 35c moves water-repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g from the standby position to the processing position. Then, amphipathic liquid valve 33g is opened, and amphipathic liquid nozzle 31g begins discharging IPA. The IPA discharged from amphipathic liquid nozzle 31g collides with the top surface of substrate W, which is rotating at the first pre-water-repellent supply speed, and then flows outward along the top surface of substrate W. This replaces the deionized water on substrate W with IPA, forming a liquid film of IPA that covers the entire top surface of substrate W. After a predetermined time has elapsed since amphipathic liquid valve 33g was opened, amphipathic liquid valve 33g is closed.

[0098] Next, a pre-water-repellent hydrophobic liquid supplying step (step S8 in FIG. 7) is performed in which toluene, which is an example of a hydrophobic liquid, is supplied onto the upper surface of the substrate W.

[0099] Specifically, with at least one guard 24 in the upper position and the water-repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the hydrophobic liquid valve 33f is opened, and the hydrophobic liquid nozzle 31f begins to discharge toluene. The toluene discharged from the hydrophobic liquid nozzle 31f collides with the upper surface of the substrate W, which is rotating at the second pre-water-repellent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the IPA on the substrate W is replaced with toluene, and a liquid film of toluene is formed that covers the entire upper surface of the substrate W. When a predetermined time has elapsed since the hydrophobic liquid valve 33f was opened, the hydrophobic liquid valve 33f is closed.

[0100] Next, a water repellent agent supplying step (step S9 in FIG. 7) of supplying a water repellent agent-containing liquid onto the upper surface of the substrate W is performed.

[0101] Specifically, with at least one guard 24 in the upper position and the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the water repellent agent valve 33e is opened, and the water repellent agent nozzle 31e begins to discharge the water repellent agent-containing liquid. The water repellent agent-containing liquid discharged from the water repellent agent nozzle 31e collides with the upper surface of the substrate W, which is rotating at the water repellent agent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the toluene on the substrate W is replaced with the water repellent agent-containing liquid, and a liquid film of the water repellent agent-containing liquid is formed to cover the entire upper surface of the substrate W. When a predetermined time has elapsed since the water repellent agent valve 33e was opened, the water repellent agent valve 33e is closed.

[0102] Next, a post-water-repellent hydrophobic liquid supplying step (step S10 in FIG. 7) is performed in which toluene, which is an example of a hydrophobic liquid, is supplied onto the upper surface of the substrate W.

[0103] Specifically, with at least one guard 24 in the upper position and the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the hydrophobic liquid valve 33f is opened, and the hydrophobic liquid nozzle 31f begins to discharge toluene. The toluene discharged from the hydrophobic liquid nozzle 31f collides with the upper surface of the substrate W, which is rotating at the first post-water-repellent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the water repellent agent-containing liquid on the substrate W is replaced with toluene, and a liquid film of toluene is formed that covers the entire upper surface of the substrate W. When a predetermined time has elapsed since the hydrophobic liquid valve 33f was opened, the hydrophobic liquid valve 33f is closed.

[0104] Next, a post-water-repellent amphipathic liquid supplying step (step S11 in FIG. 7) is performed in which IPA, which is an example of an amphipathic liquid, is supplied onto the upper surface of the substrate W.

[0105] Specifically, with at least one guard 24 in the upper position and water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g in the processing position, amphipathic liquid valve 33g is opened, and amphipathic liquid nozzle 31g begins discharging IPA. The IPA discharged from amphipathic liquid nozzle 31g collides with the upper surface of substrate W, which is rotating at the second post-water-repellent supply speed, and then flows outward along the upper surface of substrate W. As a result, toluene on substrate W is replaced with IPA, and a liquid film of IPA is formed that covers the entire upper surface of substrate W. After a predetermined time has elapsed since the amphipathic liquid valve 33g was opened, amphipathic liquid valve 33g is closed. Then, third nozzle actuator 35c moves water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g to the standby position.

[0106] Next, a water supplying step (step S12 in FIG. 7) is performed in which pure water, which is an example of a water-containing liquid, is supplied to the upper surface of the substrate W.

[0107] Specifically, with at least one guard 24 in the upper position, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d from the standby position to the processing position. Then, second rinse liquid valve 33d is opened, and second rinse liquid nozzle 31d begins to discharge deionized water. The deionized water discharged from second rinse liquid nozzle 31d collides with the upper surface of substrate W, which is rotating at the water supply speed, and then flows outward along the upper surface of substrate W. As a result, IPA on substrate W is replaced with deionized water, and a liquid film of deionized water is formed that covers the entire upper surface of substrate W. When a predetermined time has elapsed since second rinse liquid valve 33d was opened, second rinse liquid valve 33d is closed. Then, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d to the standby position.

[0108] Next, a water removal step (step S13 in FIG. 7) is performed in which the pure water is removed from the upper surface of the substrate W to expose the upper surface of the substrate W. Thereafter, a condensation step (step S14 in FIG. 7) is performed in which condensation occurs on the upper surface of the substrate W. The water removal step and the condensation step will be described later.

[0109] Next, a drying step (step S15 in FIG. 7) is performed in which the substrate W is dried by rotating the substrate W.

[0110] Specifically, the spin motor 13 accelerates the substrate W in the rotation direction, and rotates the substrate W at the highest drying speed (e.g., several thousand rpm) in the example of substrate W processing shown in FIG. 7. When the spin motor 13 starts rotating the substrate W at high speed, the liquid splashes outward from the substrate W and is removed from the substrate W. This dries the substrate W. When a predetermined time has elapsed since the high-speed rotation of the substrate W started, the spin motor 13 stops rotating. This stops the rotation of the substrate W (step S16 in FIG. 7).

[0111] Next, an unloading step (step S17 in FIG. 7) of unloading the substrate W from the chamber 4 is performed.

[0112] Specifically, when at least one guard 24 is disposed in the upper position, all of the guards 24 are lowered to the lower position. With the chuck pins 11 releasing their grip on the substrate W, the center robot CR supports the substrate W supported by the chuck pins 11 with the hand Hc, and retracts the hand Hc together with the substrate W from inside the chamber 4. As a result, the processed substrate W is unloaded from the chamber 4.

[0113] Next, the water removal process and the condensation process will be described.

[0114] 8A, 8B, 8C, 8D, 8E, 8F, 8G, 8H, and 8I are schematic cross-sectional views for explaining an example of processing of the substrate shown in FIG. 7. FIG. 9A is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in the Wenzel state. FIG. 9B is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in the Cassie-Baxter state. In the following description, unless otherwise specified, the upper surface of the substrate W includes the surface of the pattern PA.

[0115] In the example of the processing of the substrate W described above, after supplying a water-repellent agent-containing liquid, pure water, which is an example of a water-containing liquid, is supplied. As a result, the entire upper surface of the substrate W is covered with a liquid film of pure water, and the recess Q1 is filled with the liquid containing pure water. Fig. 8A shows a state in which the upper surface of the substrate W is covered with a liquid film of the water-repellent agent-containing liquid. Fig. 8B shows a state in which the upper surface of the substrate W is covered with a liquid film of pure water.

[0116] As shown in FIG. 8A, the water-repellent-agent-containing liquid on the substrate W contacts not only the end faces s1 and side faces s2 of the convex portions P1 but also the bottom faces s3 of the concave portions Q1. The water-repellent agent contained in the water-repellent-agent-containing liquid adheres to the upper surface of the substrate W, such as the end faces s1 of the convex portions P1, and forms a water-repellent film R1 on at least a portion of the upper surface of the substrate W. If the water-repellent agent is a silylating agent, the hydrogen atoms of the hydroxyl groups exposed on the upper surface of the substrate W are substituted with silyl groups containing a silicon atom and multiple methyl groups, and the multiple silyl groups form the water-repellent film R1. This enhances the water-repellent properties of the upper surface of the substrate W. Note that FIG. 8A depicts a boundary between the water-repellent-agent-containing liquid and the water-repellent film R1, but in reality, no such boundary exists.

[0117] After the upper surface of the substrate W is covered with a liquid film of pure water, a water removal process (step S13 in FIG. 7) is performed in which the pure water is removed from the upper surface of the substrate W by rotating the substrate W while holding it horizontally, as shown in FIG. 8C.

[0118] When the pure water is removed from the top surface of the substrate W, at least a portion of the top surface of the substrate W is exposed. At this time, the entire top surface of the substrate W may be exposed, or only a portion of the top surface of the substrate W may be exposed. In the former case, the entire top surface of the substrate W may be dry or wet, or only a portion of the top surface of the substrate W may be dry and only the remaining portion of the top surface of the substrate W may be wet. In other words, as long as at least a portion of the top surface of the substrate W is exposed, droplets or a liquid film may remain on the top surface of the substrate W. After the pure water is removed from the top surface of the substrate W, the pure water may remain in at least one recess Q1, or may disappear from all recesses Q1. Figure 8C shows an example of the former case.

[0119] After the pure water is removed from the upper surface of the substrate W, a condensation process (step S14 in FIG. 7) is performed to generate condensation on the upper surface of the substrate W, as shown in FIG. 8D. Condensation on the substrate W may be generated by cooling the substrate W to a temperature equal to or lower than the dew point temperature of the atmosphere in contact with the substrate W, or by increasing the temperature and humidity of the atmosphere in contact with the substrate W until the dew point temperature of the atmosphere in contact with the substrate W is equal to or higher than the temperature of the substrate W. While condensation is being generated on the upper surface of the substrate W, the substrate W may be rotated or may be stationary.

[0120] When cooling the substrate W, any one of a gas, a liquid, and a solid that is cooler than the substrate W may be brought into contact with the substrate W, or two or more of these may be brought into contact with the substrate W. In this case, a fluid (at least one of a gas and a liquid) discharged from at least one of the lower nozzle 31h and the central opening 31i shown in FIG. 2 may be brought into contact with the substrate W, or the heating / cooling plate 42 shown in FIGS. 3 and 4 may be brought into contact with the substrate W. The lower nozzle 31h, the central opening 31i, and the heating / cooling plate 42 are all examples of condensation generators. The temperature of the fluid discharged from the lower nozzle 31h and the central opening 31i may be any value as long as it is lower than room temperature. The same applies to the temperature of the heating / cooling plate 42. The temperature of the fluid and the temperature of the heating / cooling plate 42 may be 5°C or less.

[0121] When increasing the temperature and humidity of the atmosphere in contact with the substrate W, high-humidity gas generated by a humidifier located outside the chamber 4 may be supplied into the chamber 4, or a humidifier located inside the chamber 4 may generate high-humidity gas. High-humidity gas generated by a humidifier located outside the chamber 4 may be supplied into the chamber 4 while another humidifier located inside the chamber 4 generates high-humidity gas. High-humidity gas is gas whose temperature and humidity are higher than those inside the chamber 4. A humidifier is another example of a condensation generator.

[0122] 3 and 4, the substrate W can be cooled by switching the chuck pins 11 from the closed state to the open state while the spin motor 13 is stopped, and then moving the heating / cooling plate 42 from the lower position to the upper position. In this manner, the substrate W supported by the chuck pins 11 is lifted by the heating / cooling plate 42. As a result, the substrate W rests horizontally on the heating / cooling plate 42. The substrate W is cooled by contact with the heating / cooling plate 42. The temperature of the heating / cooling plate 42 may decrease simultaneously with the contact of the heating / cooling plate 42 with the substrate W, or may decrease before or after the contact of the heating / cooling plate 42 with the substrate W.

[0123] When the temperature of the substrate W is below the dew point temperature of the atmosphere in contact with the substrate W, condensation occurs on the top, bottom, and edge surfaces of the substrate W (hereinafter also referred to as the top surface, etc., of the substrate W). As a result, moisture in the atmosphere in contact with the substrate W turns into tiny droplets on the top surface, etc., of the substrate W, and the tiny droplets adhere to the top surface, etc., of the substrate W. In other words, droplets are generated everywhere within the interface between the substrate W and the atmosphere. The surfaces of the convex portions P1 and the inner surfaces of the concave portions Q1 are included in this interface. In Figures 8D, 8E, 8F, and 8G, circular shapes in contact with the water-repellent film R1 represent droplets generated by condensation. Water generated by condensation is also called condensed water or dew water.

[0124] If the temperature of the substrate W continues to be at or below the dew point temperature, droplets of condensed water grow (increase in size) on the upper surface of the substrate W, and multiple droplets of condensed water combine together, as shown in Figures 8E and 8F. If pure water remains on the upper surface of the substrate W before condensation occurs on the substrate W, the droplets of pure water grow on the upper surface of the substrate W, and multiple droplets of pure water combine together or with droplets of condensed water. As a result, larger droplets of water (droplets containing at least one of condensed water and pure water) are formed on the upper surface of the substrate W.

[0125] As water droplets grow and / or combine within the recess Q1, the space within the recess Q1 gradually decreases, and the surface of the water droplet within the recess Q1 gradually approaches the entrance of the recess Q1. As water droplets grow and / or combine at the tip of the protrusion P1, the surface of the water droplet on the tip of the protrusion P1 gradually approaches the entrance of the recess Q1. As condensation continues, the water droplet within the recess Q1 combines with the water droplet outside the recess Q1 (the water droplet on the tip of the protrusion P1) and is pulled out of the recess Q1, as shown in FIG. 8G. Furthermore, because the upper surface of the substrate W is highly water-repellent and the surface tension of water is high, a force is applied from the inner surface of the recess Q1 to the water droplet within the recess Q1, moving the water droplet out of the recess Q1. As a result, all or almost all of the water is expelled from at least one recess Q1, as shown in FIG. 8H. The thick black arrow in FIG. 8G indicates that the water droplet within the recess Q1 is moving out of the recess Q1.

[0126] It has been reported that when tiny water droplets combine on a highly water-repellent solid surface, the resulting droplets jump to a higher position than where the combination began. This jumping phenomenon can cause the droplets to be expelled from the recess Q1. When droplets that overflow from the recess Q1 combine with each other, a force that moves the droplets out of the recess Q1 can be generated. In this case, the droplets are expelled from the recess Q1 even if there are no droplets on the tip of the protrusion P1.

[0127] When the temperature of the substrate W is maintained at or below the dew point of the atmosphere in contact with the substrate W, at least one of the above-mentioned phenomena occurs. This causes water droplets to be discharged from the recessed portion Q1 and remain on the protruding portion P1. That is, one or more water droplets are supported on the upper surface of the substrate W in a Cassie-Baxter state rather than a Wenzel state. As shown in Figure 8H, the Cassie-Baxter state is a state in which the recessed portion Q1 is filled with air and one or more water droplets are supported by the air in the recessed portion Q1 and the tips of the protruding portion P1. When the water droplets on the substrate W are in the Cassie-Baxter state, the contact angle of water with respect to the upper surface of the substrate W to which the water repellent-containing liquid has been applied may be 100 degrees or more, preferably 140 degrees or more.

[0128] As shown in FIG. 9A, the rough surface is a solid surface provided with a plurality of recesses Q1 and a plurality of protrusions P1. The recesses Q1 are recessed from the tips of the protrusions P1. The protrusions P1 protrude from the bottom of the recesses Q1. The bottom of the recesses Q1 corresponds to the base of the protrusions P1. The tips of two adjacent protrusions P1 form the entrance of the recess Q1 located between them.

[0129] As shown in FIG. 9A, the Wenzel state (hereinafter also referred to as the W state) is a state in which a water droplet on a horizontal rough surface penetrates into a recess Q1. As shown in FIG. 9B, the Cassie-Baxter state (hereinafter also referred to as the CB state) is a state in which the recess Q1 is filled with air and the water droplet is supported by the tips of the protrusions P1. In the CB state, the water droplet is supported by the air in the recess Q1 and the tips of the protrusions P1. In other words, when a water droplet is placed on a horizontal rough surface under normal temperature and pressure (room temperature and 1 atmosphere), the tips of the protrusions P1 come into contact with the water droplet while the bottom of the recess Q1 is separated from the water droplet. Room temperature is, for example, a constant or approximately constant temperature within the range of 10 to 30°C.

[0130] Whether a water droplet on a rough surface adopts the W or CB state depends on factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface texture of the rough surface. It is thought that the higher the surface tension of the liquid and the lower the surface free energy of the rough surface (the more water-repellent the rough surface is), the more likely the water droplet on the rough surface will adopt the CB state.

[0131] Pure water is a liquid with high surface tension. The water-repellent agent contained in the water-repellent-containing liquid is a substance that increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end surface s1 of the convex portion P1 to a value exceeding 90 degrees, and the upper surface of the substrate W is rough. Therefore, the surface free energy of the upper surface of the substrate W is low (the upper surface of the substrate W has high water repellency). Therefore, when the amphipathic liquid on the substrate W is replaced with pure water, the pure water can contact the upper surface of the substrate W in a CB state. In other words, during the process of replacing the amphipathic liquid on the substrate W with pure water, at least one of the amphipathic liquid and the pure water can be discharged from the concave portion Q1, and at least a portion of the concave portion Q1 can be filled with air.

[0132] IPA is an example of an amphipathic liquid. The IPA in the recess Q1 is gradually diluted by mixing with the pure water. As a result, the IPA in the recess Q1 is replaced with pure water. Even if the pure water is in a CB state and can contact the top surface of the substrate W, there is a period when the pure water is in a W state, that is, when the recess Q1 is filled with pure water and is in contact with the top surface of the substrate W. The pure water may spontaneously change from the W state to the CB state, but the pure water may not transition from the W state to the CB state unless some energy is applied to at least one of the substrate W and the pure water.

[0133] In contrast, if condensation is generated on the upper surface of the substrate W after the liquid film of pure water is removed from the upper surface of the substrate W, one or more water droplets will be supported on the upper surface of the substrate W in the CB state, as described above. When liquid such as pure water evaporates in the recess Q1, a collapsing force that causes the protrusion P1 to collapse may be applied to the protrusion P1. By moving the liquid such as pure water from inside the recess Q1 to outside, the amount of liquid that evaporates in the recess Q1 can be reduced. This can eliminate or reduce the collapse of the pattern PA (collapse of the protrusion P1) caused by the evaporation of the liquid in the recess Q1.

[0134] After one or more water droplets are supported on the upper surface of the substrate W in a CB state, that is, after a predetermined time has elapsed since condensation began on the substrate W, a drying step (step S15 in FIG. 7) is performed in which the substrate W is rotated while being held horizontally, as shown in FIG. 8I, to remove one or more water droplets from the upper surface of the substrate W. The thick black arrows in FIG. 8I indicate that the water droplets are moving relative to the upper surface of the substrate W. This removes liquid not only from within the recess Q1 but also from outside the recess Q1, drying the upper surface of the substrate W. If the lower surface and edge surfaces of the substrate W are wet with condensation, they also dry. After the substrate W has dried, the substrate W is transferred from the spin chuck 10 as described above.

[0135] The rotation speed of the substrate W in the drying step (step S15 in FIG. 7) (the aforementioned drying speed) may be equal to the rotation speed of the substrate W in the water removal step (step S13 in FIG. 7) (water removal speed), or may be greater than or less than the water removal speed. The period during which the substrate W is rotated at the drying speed may be equal to the period during which the substrate W is rotated at the water removal speed, or may be longer or shorter than that period. In other words, the period during which the drying step is performed may be equal to the period during which the water removal step is performed, or may be longer or shorter than that period.

[0136] In at least one of the water removal step and the drying step, the substrate W may be tilted relative to a horizontal plane to remove liquid such as pure water from the substrate W. When the substrate W is tilted in both the water removal step and the drying step, the tilt angle of the substrate W in the drying step may be equal to, or larger or smaller than, the tilt angle of the substrate W in the water removal step.

[0137] When tilting the substrate W, the tilt actuator may position a pusher, which is movable between an upper position and a lower position, at the upper position. The upper position is a position where the pusher lifts only a portion of the substrate W while in contact with the lower surface of the stationary substrate W, thereby tilting the substrate W supported by the spin chuck 10. The lower position is a position where the pusher is separated from the substrate W, and the substrate W is supported horizontally by the spin chuck 10. The spin motor 13 is an example of a liquid removal actuator. The tilt actuator is another example of a liquid removal actuator.

[0138] When the temperature of the substrate W is below the dew point temperature of the atmosphere in contact with the substrate W, condensed water slowly accumulates on the substrate W. During the drying process (step S15 in FIG. 7), the temperature of the substrate W may be below the dew point temperature or may be above the dew point temperature. If the temperature of the substrate W is raised to a value above the dew point temperature before the drying process is completed (before the rotation of the substrate W is stopped), the time required to dry the substrate W can be shortened. Alternatively, the dried substrate W can be prevented from becoming wet due to condensation.

[0139] When cooling the substrate W, the temperature of the substrate W may be raised to room temperature or near room temperature by heating the substrate W with a fluid discharged from at least one of the lower nozzle 31h and the central opening 31i shown in Fig. 2, or by the heating / cooling plate 42 shown in Fig. 3 and Fig. 4. When raising the temperature and humidity of the atmosphere in contact with the substrate W, a gas having a temperature and humidity lower than that of the atmosphere may be supplied into the chamber 4.

[0140] 3 and 4 in the condensation step (step S14 in FIG. 7) and rotate the substrate W in the drying step (step S15 in FIG. 7), the substrate W may be moved from the heating and cooling plate 42 to the plurality of chuck pins 11, and then the spin motor 13 may be rotated with the plurality of chuck pins 11 pressed against the edge surface of the substrate W. In this case, the substrate W may be heated by the heating and cooling plate 42 before being moved from the heating and cooling plate 42 to the plurality of chuck pins 11, thereby raising the temperature of the substrate W to room temperature or nearby. In this way, the temperature of the substrate W can be raised to a value above the dew point temperature before the drying step is performed.

[0141] Next, the effects of this embodiment will be described.

[0142] In this embodiment, a water-repellent agent-containing liquid is supplied to the surface of the substrate W. A pattern PA including convex portions P1 and concave portions Q1 is formed on the surface of the substrate W. Therefore, the surface of the substrate W is not smooth but rough. When the water-repellent agent-containing liquid is supplied to a horizontal, smooth surface made of the same material as the end surface s1 of the convex portion P1, the contact angle of water with the smooth surface increases to a value greater than 90 degrees. According to Wenzel's equation, when the contact angle of water with a smooth surface exceeds 90 degrees, the contact angle of water with a rough surface made of the same material as the smooth surface exceeds the contact angle of water with the smooth surface. Therefore, when the water-repellent agent-containing liquid is supplied to the surface of the substrate W, the contact angle of water with the surface of the substrate W increases to a value well above 90 degrees.

[0143] After the water-repellent agent-containing liquid is supplied to the surface of the substrate W, a water-containing liquid such as pure water is supplied to the surface of the substrate W. Thereafter, the water-containing liquid is removed from the surface of the substrate W to expose at least a portion of the surface of the substrate W. In this state, condensation is generated on the surface of the substrate W. As a result, moisture in the atmosphere in contact with the substrate W turns into water droplets on the surface of the substrate W, and the water droplets adhere to the surface of the substrate W. If condensation continues, the water droplets grow or multiple water droplets combine together. If the water-containing liquid remains on the surface of the substrate W, the droplets of the water-containing liquid grow or multiple water-containing liquid droplets or droplets of the water-containing liquid combine together.

[0144] The water repellency of the surface of the substrate W is increased by the supply of the water repellent-containing liquid. Therefore, a force that expels the water droplets from the recess Q1 acts on the water droplets in the recess Q1 from the inner surface of the recess Q1. The water droplets in the recess Q1 are expelled from the recess Q1 as they grow and combine with other droplets. If water-containing liquid remains in the recess Q1, the water-containing liquid is expelled from the recess Q1 by a similar phenomenon. Therefore, while condensation is occurring, the water in the recess Q1 gradually decreases, and the water outside the recess Q1 gradually increases.

[0145] When a predetermined time has elapsed since the onset of condensation, water droplets are removed from the surface of the substrate W. If water-containing liquid remains on the surface of the substrate W, the water-containing liquid is also removed from the surface of the substrate W. This dries the surface of the substrate W. Before drying the surface of the substrate W, water is drained from the recesses Q1. In some cases, all or almost all of the water is drained from the recesses Q1. Therefore, it is possible to eliminate or reduce the amount of water remaining in the recesses Q1 after the surface of the substrate W is dried, and it is possible to eliminate or reduce the collapse of the pattern PA (collapse of the protrusions P1) caused by evaporation of the water.

[0146] In this embodiment, after the water-repellent-agent-containing liquid is supplied, condensation occurs with at least a portion of the surface of the substrate W exposed from the water-containing liquid. Water droplets generated by the condensation adhere to the inner surface of the recessed portion Q1 of the substrate W and the surface of the protruding portion P1 of the substrate W. If the condensation continues, the water droplets grow in the recessed portion Q1 or multiple water droplets combine in the recessed portion Q1. The same applies when the water-containing liquid remains in the recessed portion Q1. Because the inner surface of the recessed portion Q1 repels water (here, at least one of condensed water and the water-containing liquid), the water droplets in the recessed portion Q1 are discharged to the outside of the recessed portion Q1 as they grow or combine with other droplets. If the water-containing liquid remains in the recessed portion Q1, the water-containing liquid is discharged to the outside of the recessed portion Q1 by a similar phenomenon. This makes it possible to eliminate or reduce the water remaining in the recessed portion Q1.

[0147] In this embodiment, removal of water droplets from the surface of the substrate W begins when at least a portion of the recess Q1 is filled with air and the water droplets are supported by the air in the recess Q1 and the protrusion P1. In other words, because the surface of the substrate W is highly water-repellent and the surface tension of water is high, when condensation occurs, the water droplets are supported on the surface of the substrate W in a Cassie-Baxter state. Drying of the substrate W begins in this state. When the water droplets are in a Cassie-Baxter state, they do not or barely enter the recess Q1. Therefore, it is possible to eliminate or reduce the water remaining in the recess Q1 after the surface of the substrate W is dried.

[0148] In this embodiment, the temperature of the substrate W is lowered by cooling the substrate W. When the temperature of the substrate W drops below the dew point temperature of the atmosphere in contact with the substrate W, the moisture in the atmosphere turns into water droplets on the surface of the substrate W, and the water droplets adhere to the surface of the substrate W. This causes condensation to occur on the surface of the substrate W. If the temperature and humidity of the atmosphere in contact with the substrate W are increased, condensation will also occur on solid surfaces other than the substrate W. Cooling the substrate W can eliminate or reduce such condensation, and the moisture in the atmosphere can be efficiently attached to the surface of the substrate W.

[0149] In this embodiment, the substrate W is cooled while being stationary, rather than while being moved. When the substrate W moves, an air current may be generated. Such an air current may prevent condensation on the substrate W and may also evaporate water adhering to the substrate W. If the substrate W is cooled while being stationary, it is possible to reliably generate condensation on the surface of the substrate W while reducing the amount of water evaporated from the substrate W.

[0150] In this embodiment, the water-repellent-agent-containing liquid on the surface of the substrate W is replaced with a hydrophobic liquid, and the hydrophobic liquid on the surface of the substrate W is replaced with an amphipathic liquid. When the water-repellent agent contained in the water-repellent-agent-containing liquid comes into contact with water, unwanted substances may be generated in the water-repellent-agent-containing liquid. By replacing the water-repellent-agent-containing liquid with a hydrophobic liquid in which the solubility of water is lower than that of the amphipathic liquid, the generation of such unwanted substances can be prevented or the amount of such substances generated can be reduced. In addition, the amount of water-repellent-agent-containing liquid remaining in the water-containing liquid can be reduced compared to when the water-repellent-agent-containing liquid on the surface of the substrate W is replaced with an amphipathic liquid.

[0151] In this embodiment, the surface of the substrate W is oxidized by supplying a chemical solution to the surface of the substrate W. As a result, at least a portion of the surface of the substrate W is terminated with hydroxy groups (OH groups). When the surface of the substrate W is oxidized with the chemical solution, the number of hydroxy groups exposed on the surface of the substrate W increases. If the water repellent agent is a silylating agent, the hydrogen atoms of the hydroxy groups are substituted with silyl groups of the water repellent agent. Therefore, by supplying the chemical solution to the surface of the substrate W, the water repellency of the surface of the substrate W can be efficiently increased.

[0152] Furthermore, the chemical liquid on the surface of the substrate W is replaced with a water-containing liquid as a rinse liquid, rather than with a water-repellent-containing liquid. Thereafter, the water-containing liquid on the surface of the substrate W is replaced with an amphipathic liquid, and the amphipathic liquid on the surface of the substrate W is replaced with a hydrophobic liquid. Even if any water-containing liquid remains after replacing the water-containing liquid with the amphipathic liquid, this water-containing liquid diffuses into the amphipathic liquid on the surface of the substrate W. Then, the amphipathic liquid is replaced with a hydrophobic liquid. The hydrophobic liquid is a liquid in which water is less soluble than in the amphipathic liquid. Therefore, water remaining on the surface of the substrate W can be eliminated or reduced.

[0153] When the water-repellent agent contained in the water-repellent-containing liquid comes into contact with water, unwanted substances may be generated in the water-repellent-containing liquid. Since the water-containing liquid used as a rinse liquid is gradually replaced with the amphipathic liquid and the hydrophobic liquid, the water-repellent-containing liquid can be supplied to the surface of the substrate W with no water remaining on the substrate W or with only a very small amount of water remaining. Therefore, the water repellency of the surface of the substrate W can be increased while preventing or reducing the generation of unwanted substances.

[0154] Next, another embodiment will be described.

[0155] Instead of ejecting the chemical liquid, rinse liquid, water repellent agent-containing liquid, hydrophobic liquid, and amphipathic liquid from separate nozzles, two or more of these may be ejected from a single nozzle.

[0156] The water-containing liquid supplied to the upper surface of the substrate W in the water supplying step (step S12 in FIG. 7) may not be pure water, but may be a foamable water-containing liquid that foams under normal temperature and pressure conditions, such as carbonated water. In this case, the transition of the foamable water-containing liquid from the Wenzel state to the Cassie-Baxter state can be promoted by the gas generated from the foamable water-containing liquid.

[0157] Instead of supplying a hydrophobic liquid such as toluene and then supplying the water-repellent agent-containing liquid, the water-repellent agent-containing liquid may be supplied onto the upper surface of the substrate W that is covered with an amphipathic liquid such as IPA. In other words, the supply of the hydrophobic liquid between the supply of the amphipathic liquid and the supply of the water-repellent agent-containing liquid may be omitted.

[0158] Instead of supplying the hydrophobic liquid after supplying the water-repellent agent-containing liquid, the amphipathic liquid may be supplied onto the upper surface of the substrate W covered with the water-repellent agent-containing liquid. In other words, the supply of the hydrophobic liquid between the supply of the water-repellent agent-containing liquid and the supply of the amphipathic liquid may be omitted.

[0159] The substrate processing apparatus 1 may be a batch type apparatus that processes a plurality of substrates W at once.

[0160] As shown in Figure 10, the batch-type substrate processing apparatus 1 includes a lifter 51 that holds multiple substrates W, a lifting actuator 52 that moves the lifter 51 up and down in parallel between an upper position and a lower position, and an immersion tank 53 that collects processing liquid in which the multiple substrates W held by the lifter 51 located in the lower position (the position shown in Figure 10) are immersed.

[0161] The batch-type substrate processing apparatus 1 further includes a processing liquid nozzle 54 that supplies the processing liquid into the immersion tank 53, a processing liquid pipe 55 that guides the processing liquid discharged from the processing liquid nozzle 54, a processing liquid valve 56 that switches between an open state that allows the processing liquid to flow through the processing liquid pipe 55 toward the processing liquid nozzle 54 and a closed state that stops the processing liquid, a pump 57 that sends the processing liquid in the processing liquid pipe 55 to the processing liquid nozzle 54, and a filter 58 that removes foreign matter from the processing liquid supplied from the processing liquid pipe 55 to the processing liquid nozzle 54. The batch-type substrate processing apparatus 1 may further include an overflow tank 59 that collects the processing liquid overflowing from the immersion tank 53. In this case, the processing liquid pipe 55 may supply the processing liquid in the overflow tank 59 to the processing liquid nozzle 54.

[0162] When the processing liquid nozzle 54 discharges the processing liquid, the processing liquid accumulates in the immersion tank 53. In this state, when the lifting actuator 52 moves the lifter 51 to the lower position, all of the substrates W held by the lifter 51 are positioned below the surface (liquid level) of the processing liquid in the immersion tank 53. The processing liquid nozzle 54 may discharge multiple processing liquids, such as a water repellent-containing liquid, individually, or may discharge only one type of processing liquid. In the latter case, the substrate processing apparatus 1 may be provided with multiple sets of lifters 51, lifting actuators 52, immersion tanks 53, and processing liquid nozzles 54.

[0163] The lifter 51 is an example of a substrate holder. The lifting actuator 52 is an example of a liquid removal actuator. When the lifting actuator 52 moves the lifter 51 from a lower position to an upper position, all of the substrates W held by the lifter 51 move above the surface of the processing liquid in the immersion tank 53. As the lifter 51 rises, the processing liquid flows down from the substrates W. As a result, the processing liquid is removed from the substrates W.

[0164] The substrate processing apparatus 1 is not limited to an apparatus for processing a disk-shaped substrate W, but may be an apparatus for processing a polygonal substrate W.

[0165] Any two or more of the above-described configurations may be combined. Any two or more of the above-described steps may be combined.

[0166] Although the embodiments of the present invention have been described in detail, these are merely examples used to clarify the technical contents of the present invention, and the present invention should not be construed as being limited to these examples. The spirit and scope of the present invention are limited only by the appended claims. [Explanation of symbols]

[0167] 1: substrate processing apparatus, 3: control device, 10: spin chuck, 13: spin motor, 31a: first chemical liquid nozzle, 31b: first rinse liquid nozzle, 31c: second chemical liquid nozzle, 31d: second rinse liquid nozzle, 31e: water repellent agent nozzle, 31f: hydrophobic liquid nozzle, 31g: amphipathic liquid nozzle, 31h: lower nozzle, 31i: central opening, 33a: first chemical liquid valve, 33b: first rinse liquid valve, 33c: second chemical liquid valve, 33d: second rinse liquid valve, 33e: water repellent agent valve, 33f: hydrophobic liquid valve, 33g: amphipathic liquid valve, 33h: rinse liquid valve, 33i: inert gas valve, 42: heating / cooling plate, 43: Peltier element, 51: lifter, 52: lifting actuator, 53: immersion tank, 54: processing liquid nozzle, 55: processing liquid piping, 56: processing liquid valve, P1: convex portion, PA: pattern, Q1: concave portion, R1: water repellent film, W: substrate, s1: end face, s2: side face, s3: bottom face, s4: base layer

Claims

1. A substrate processing method for processing a substrate having a pattern including convex portions and concave portions formed on a surface thereof, comprising: a water-repellent supplying step of supplying a water-repellent-containing liquid onto the surface of the substrate, the water-repellent-containing liquid increasing the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees; a water supplying step of supplying a water-containing liquid onto the surface of the substrate after supplying the water-repellent agent-containing liquid onto the surface of the substrate; a water removal step of removing the water-containing liquid from the surface of the substrate to expose at least a portion of the surface of the substrate; a condensation process of causing condensation on the surface of the substrate, thereby causing water droplets to adhere to the surface of the substrate; a drying step of removing the water droplets from the surface of the substrate to dry the surface of the substrate.

2. The substrate processing method according to claim 1 , wherein the condensation step includes the step of causing condensation to occur on the surface of the substrate, thereby causing the water droplets to adhere to at least the inner surface of the recess.

3. 3. The substrate processing method according to claim 1, wherein the drying step includes a step of starting to remove the water droplets from the surface of the substrate in a state in which at least a portion of the recess is filled with air and the water droplets are supported by the air in the recess and the protrusion.

4. 3. The substrate processing method according to claim 1, wherein the condensation step includes a step of cooling the substrate.

5. The substrate processing method according to claim 4 , wherein the condensation step includes the step of cooling the substrate while keeping the substrate stationary.

6. The substrate processing method includes: a post-water-repellent hydrophobic liquid supplying step of supplying a hydrophobic liquid that is soluble in the water-repellent agent-containing liquid onto the surface of the substrate, thereby replacing the water-repellent agent-containing liquid on the surface of the substrate with the hydrophobic liquid; a post-water-repellent amphipathic liquid supplying step of supplying an amphipathic liquid, which has a higher solubility in water than the hydrophobic liquid and is soluble in the hydrophobic liquid, onto the surface of the substrate, thereby replacing the hydrophobic liquid on the surface of the substrate with the amphipathic liquid, 3. The substrate processing method according to claim 1, wherein the water supplying step is a step of replacing the amphipathic liquid on the surface of the substrate with the water-containing liquid by supplying the water-containing liquid, which has a surface tension greater than that of the amphipathic liquid and is soluble in the amphipathic liquid, to the surface of the substrate.

7. The substrate processing method includes: a chemical solution supplying step of supplying a chemical solution that oxidizes the surface of the substrate to the surface of the substrate; a rinse liquid supplying step of supplying the water-containing liquid as a rinse liquid onto the surface of the substrate, thereby replacing the chemical liquid on the surface of the substrate with the water-containing liquid; a pre-water-repellent amphiphilic liquid supplying step of supplying an amphiphilic liquid that is soluble in the water-containing liquid onto the surface of the substrate, thereby replacing the water-containing liquid on the surface of the substrate with the amphiphilic liquid; a pre-water-repellent hydrophobic liquid supplying step of supplying a hydrophobic liquid, which has a lower solubility in water than the amphipathic liquid and is soluble in the amphipathic liquid, to the surface of the substrate, thereby replacing the amphipathic liquid on the surface of the substrate with the hydrophobic liquid, 3. The substrate processing method according to claim 1, wherein the water-repellent supplying step is a step of replacing the hydrophobic liquid on the surface of the substrate with the water-repellent-containing liquid by supplying the water-repellent-containing liquid to the surface of the substrate.

8. a substrate holder for holding a substrate on whose surface a pattern including protrusions and recesses is formed; at least one nozzle that individually supplies a plurality of treatment liquids to the surface of the substrate held by the substrate holder by individually discharging the treatment liquids, the treatment liquid including a water-repellent-containing liquid that increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end face of the convex portion to a value exceeding 90 degrees, and a water-containing liquid; at least one valve that causes the at least one nozzle to individually eject the plurality of treatment liquids; at least one liquid removal actuator that moves the substrate to remove the processing liquid from the surface of the substrate held by the substrate holder to expose at least a portion of the surface of the substrate; a condensation generator that generates condensation on the surface of the substrate held by the substrate holder, thereby causing water droplets to adhere to the surface of the substrate; a controller for controlling the at least one valve, the liquid removal actuator, and the condensation generator; The control device a water repellent supplying step of supplying the water repellent-containing liquid to the surface of the substrate; a water supplying step of supplying the water-repellent-agent-containing liquid onto the surface of the substrate, and then supplying the water-containing liquid onto the surface of the substrate; a water removal step of removing the water-containing liquid from the surface of the substrate by the at least one liquid removal actuator, thereby exposing at least a portion of the surface of the substrate; a condensation process of causing condensation on the surface of the substrate, thereby causing water droplets to adhere to the surface of the substrate; a drying step of drying the surface of the substrate by removing the water droplets from the surface of the substrate with the at least one liquid removal actuator.

9. The substrate processing apparatus according to claim 8 , wherein the condensation step includes the step of causing condensation to occur on the surface of the substrate, thereby causing the water droplets to adhere to at least the inner surface of the recess.

10. 10. The substrate processing apparatus according to claim 8, wherein the drying step includes a step of starting removal of the water droplets from the surface of the substrate in a state in which at least a portion of the recess is filled with air and the water droplets are supported by the air in the recess and the protrusion.

11. The substrate processing apparatus according to claim 8 , wherein the condensation step includes a step of cooling the substrate.

12. The substrate processing apparatus according to claim 11 , wherein the condensation step includes the step of cooling the substrate while keeping the substrate stationary.

13. the at least one nozzle individually ejects a plurality of treatment liquids including the water-repellent-containing liquid, a hydrophobic liquid that dissolves in the water-repellent-containing liquid, an amphipathic liquid that has a higher solubility of water than the hydrophobic liquid and dissolves in the hydrophobic liquid, and the water-containing liquid that has a higher surface tension than the amphipathic liquid and dissolves in the amphipathic liquid; The control device the water repellent supplying step; a post-water-repellent hydrophobic liquid supplying step of supplying the hydrophobic liquid to the surface of the substrate, thereby replacing the water-repellent agent-containing liquid on the surface of the substrate with the hydrophobic liquid; a post-water-repellent amphipathic liquid supplying step of supplying the amphipathic liquid to the surface of the substrate to replace the hydrophobic liquid on the surface of the substrate with the amphipathic liquid; 10. The substrate processing apparatus according to claim 8, further comprising: a water supplying step of supplying the water-containing liquid to the surface of the substrate, thereby replacing the amphipathic liquid on the surface of the substrate with the water-containing liquid.

14. the at least one nozzle individually discharges a plurality of treatment liquids including the water-repellent-containing liquid, the water-containing liquid, a chemical liquid that oxidizes the surface of the substrate, an amphipathic liquid that dissolves in the water-containing liquid, and a hydrophobic liquid that has a lower solubility of water than the amphipathic liquid and dissolves in the amphipathic liquid; The control device a chemical solution supplying step of supplying the chemical solution to the surface of the substrate; a rinse liquid supplying step of supplying the water-containing liquid as a rinse liquid onto the surface of the substrate, thereby replacing the chemical liquid on the surface of the substrate with the water-containing liquid; a pre-water-repellent amphiphilic liquid supplying step of supplying the amphiphilic liquid to the surface of the substrate to replace the water-containing liquid on the surface of the substrate with the amphiphilic liquid; a pre-repellent hydrophobic liquid supplying step of supplying the hydrophobic liquid to the surface of the substrate, thereby replacing the amphipathic liquid on the surface of the substrate with the hydrophobic liquid; 10. The substrate processing apparatus according to claim 8, further comprising: a water-repellent supplying step of supplying the water-repellent-containing liquid to the surface of the substrate, thereby replacing the hydrophobic liquid on the surface of the substrate with the water-repellent-containing liquid.

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